CN105984929B - A kind of aluminium silicate polymer zinc composite flocculation agent and its application - Google Patents
A kind of aluminium silicate polymer zinc composite flocculation agent and its application Download PDFInfo
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- CN105984929B CN105984929B CN201610039396.XA CN201610039396A CN105984929B CN 105984929 B CN105984929 B CN 105984929B CN 201610039396 A CN201610039396 A CN 201610039396A CN 105984929 B CN105984929 B CN 105984929B
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/52—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities
- C02F1/5236—Treatment of water, waste water, or sewage by flocculation or precipitation of suspended impurities using inorganic agents
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/76—Treatment of water, waste water, or sewage by oxidation with halogens or compounds of halogens
Abstract
The invention discloses a kind of aluminium silicate polymer zinc composite flocculation agent and its applications, sodium silicate solution and excessive sulfuric acid were mixed with polysilicon acid solution before this by the composite flocculation agent, then sequentially add zinc sulfate and aluminum sulfate solution, polyacrylamide, calcium hydroxide and sodium hypochlorite reaction obtain；The composite flocculation agent, which is applied to water treatment field, can realize good decoloration turbidity removal decarburization effect, have many advantages, such as to agglomerate alumina blossom particles are larger, floc settling velocity is fast, net catch make good use of, the turbidity removal effect that decolourizes it is good, and the composite flocculation agent raw material sources are extensive, preparation is simple, can be widely applied to the industrial wastewaters such as printing and dyeing, papermaking field and municipal wastewater advanced treating field.
Description
Technical field
The present invention relates to field of waste water treatment, especially a kind of aluminium silicate polymer zinc composite flocculation agent and its application.
Background technique
As China's rapid economic development and urbanization process are accelerated, the discharge amount of municipal sewage and industrial wastewater increases year by year
It is more, how to handle a great problem that these waste water have become urban construction.Flocculation is a kind of common wastewater treatment means, in water
Occupy important position in processing, in recent years, flocculation technique was quickly grown in recent years, and the flocculant type developed is increasingly
More, flocculant can be divided into organic flocculant, inorganic flocculating agent and microbial flocculant again.Traditional inorganic flocculating agent is difficult to control water
The formation of product is solved, and inorganic polymer flocculant can make flocculating learn to control, and can prepare and be suitble to flocculation dosage form
At perfect solution have wide range of applications with pH, can handle the advantage of the water body of more different temperatures, property.Polysilicon acid
Metal salt is the combination product formed after polymerizeing traditional metal salt flocculant with silicic acid or polysilicon acid, is a kind of novel nothing
Machine polymeric flocculant.
Polysilicon acid flocculant generally has a negative electricity, therefore is acted on without charge neutrality water-borne glue body particle, mainly according to
Adsorption bridging effect aggregated particle is formed by macromolecular and forms precipitating, and polysilics acid metal salt flocculant is introduced into metal salt poly-
Polysilics acid metal salt flocculant is made in silicic acid, metal salt mainly includes aluminium salt and molysite, and zincum salts flocculant is heavy with wadding body
Fast speed drops, and moisture percentage in sewage sludge is lower, the advantages such as good purification and processing cost relative moderate.Polysilics acid metal salt can be with
The weakness that metal salt relative molecular mass is not big enough, sinking speed is slow, aggregation adsorption bridging ability is not strong enough is made up, is also made up
Polysilicon acid flocculant is unstable, does not have the weakness of charge neutrality effect to water-borne glue body, obtains people's extensive concern and continues
Research.
Polyacrylamide is the organic synthesis high polymer coagulant being most widely used in water process, has good flocculation
Ability is commonly used for including in the water process such as Industrial Wastewater Treatment, municipal sewage treatment, it can be not only used for municipal wastewater
Coagulation, it can also be used to the dehydration of sludge.Sodium hypochlorite is a kind of excellent bleaching agent and fungicide, it has broad-spectrum, makees
With advantage fast, that effect is good, and it is simple production process, cheap, it is widely used in papermaking, weaving work as bleaching agent
Industry.The patent of invention of Publication No. CN104478051A discloses a kind of preparation method of polymeric aluminium ferrum silicate flocculant, with
Tetraethyl orthosilicate is silicon source, first reacts with boiling water and generates polysilicon acid, then mixes again with aluminium salt and molysite, and polymeric silicicacid is made
Ferro-aluminum flocculant, the invention prepare polysilicon acid using boiling water, and preparation process is complicated, at high cost, it is difficult to promote, and molysite added
After amount, flocculant decolorizing effect be will be greatly reduced；The patent of invention of Publication No. CN104445236A discloses a kind of polymerization silicon
Crosslinking agent is added in sour aluminium zinc flocculant and its preparation method and application, the invention in silicate solutions, adjusts pH and obtains poly- silicon
Then acid solution sequentially adds aluminium salt and zinc salt into solution, aluminium silicate polymer zinc flocculant is made, needs additional crosslinking in the invention
Agent, and dosage is larger, pH, which is adjusted, to be required accurately, and preparation cost is higher, complex process.
It is comprehensive institute it is above-mentioned, existing polysilics acid metal salt flocculant process effect is preferable, but complex process, processing cost compared with
Height, wadding body are not sufficiently stable, therefore provide that a kind of preparation process is simple, and the stable aluminium silicate polymer zinc composite flocculation agent of wadding body has become
Urgent technical problem to be solved in the field.
Summary of the invention
In view of the above-mentioned problems, the present invention provides a kind of preparation method of aluminium silicate polymer zinc composite flocculation agent, the composite flocculation
Agent for industry and municipal wastewater process field there is good decoloration turbidity removal to remove carbon effect, the present invention is implemented as follows:
A kind of aluminium silicate polymer zinc composite flocculation agent, the composite flocculation agent obtain by the following method:
A it is) 2mol/L sulfuric acid after 10:1 is mixed by volume by sodium metasilicate and concentration that concentration is 0.3-0.5mol/L, adjusts
Section pH is 2-4, and 80-120rpm is stirred to react 30-50min, is then allowed to stand 10-20min, obtains polysilicon acid solution；
B the solution of zinc sulfate and aluminum sulfate solution that concentration is 0.2mol/L, 80-) are successively added into polysilicon acid solution
120rpm is stirred to react 10-30min, then quiet 10-20min, obtains aluminium silicate polymer zinc solution；
Polysilicon acid solution be added and solution of zinc sulfate volume ratio are 1:0.5-1.5, polysilicon acid solution and solution of zinc sulfate
Volume ratio be 1:0.5-1.5；
C) aluminium silicate polymer zinc solution is uniformly mixed with polyacrylamide, calcium hydroxide and sodium hypochlorite, 20-40rpm is anti-
20-30min is answered, 10-40min is then allowed to stand, is i.e. acquisition aluminium silicate polymer zinc composite flocculation agent；
Wherein, polyacrylamide, calcium hydroxide and the sodium hypochlorite being added it is identical in quality, aluminium silicate polymer zinc solution with
Their mass ratio is 10000:4-8.
Further, in aluminium silicate polymer zinc composite flocculation agent preparation process of the present invention, step B) the isometric sulfuric acid of middle addition
Zinc solution and aluminum sulfate solution.
Further, in aluminium silicate polymer zinc composite flocculation agent preparation process of the present invention, step C) in aluminium silicate polymer zinc solution with
The mass ratio of polyacrylamide, calcium hydroxide and sodium hypochlorite is 10000:6.
A kind of application of aluminium silicate polymer zinc composite flocculation agent as described herein in Treating Municipal Sewage and industrial wastewater.
It is described in Treating Municipal Sewage and industrial wastewater in the application of aluminium silicate polymer zinc composite flocculation agent as described herein
In application refer to, by the aluminium silicate polymer zinc composite flocculation agent by volume 0.5%-1% put into sewage in, first with 200-
The stirring 30-40s of 400rpm, then 25-40 min is stirred with the speed of 25-40rpm, it is then allowed to stand 1-2h, that is, is realized to city
The decoloration turbidity removal decarburization of sewage and industrial wastewater.
The present invention introduces polyacrylamide, sodium hypochlorite and hydroxide on the basis of original aluminium silicate polymer zinc flocculant
Calcium adds a small amount of polyacrylamide in aluminium silicate polymer zinc macromolecular substances, polysilics acid metal salt reticular structure can be enhanced, mention
High polysilics acid metal salt stability constructs inorganic organic polymer flocculant, while the adsorption bridging for improving composite flocculation agent is made
With.While a small amount of sodium hypochlorite can be such that macromolecular substances adsorb, using hypochlorous acid oxidization and blanching effect, enhance flocculant
Decolorization, a small amount of calcium hydroxide is used in preparation process, both adjustable wastewater pH, reached optimum reaction condition, together
When using calcium ion as core, absorption effluent organic matter and macromolecular substances enhance the settling property of composite flocculation agent.Compared to existing
There is technology, the beneficial effects of the present invention are embodied in:
(1) preparation method of the invention is simple, easily operated, adjusts pH at normal temperature and mixes solution, without height
Warm high pressure, additive amount is less, low in cost, and sodium metasilicate is from a wealth of sources, and composite flocculation agent is added directly in water and is mixed,
Operating process is simple；
(2) compound wadding can be enhanced in a kind of aluminium silicate polymer zinc composite flocculation agent that the present invention is prepared, polyacrylamide
Solidifying agent stability, enhances suction-operated, constructs inorganic organic polymer flocculant, and sodium hypochlorite has both oxidation and decoloration bleaching
Substance ligand complex in effect, calcium ion and water enhances flocculant sedimentation effect, is passing polysilicate-metals composite flocculant
On the basis of system, the function of its turbidity removal decarburization of decolourizing is greatly improved；
(3) the aluminium silicate polymer zinc composite flocculation agent function admirable that the present invention is prepared can synchronize decoloration turbidity removal decarburization,
It solves the problems such as previous adding of agent dosage is big, removal effect is unstable, and removal target contaminant is single, substantially increases
Engineering using effect.
Detailed description of the invention
Fig. 1 is embodiment aluminium silicate polymer zinc composite flocculation agent flocculating effect schematic diagram.
Specific embodiment
Embodiment 1 prepares aluminium silicate polymer zinc composite flocculation agent
(1) sodium silicate solution of 0.4mol/L, the dilute sulphur for being 2mol/L by the diluting concentrated sulfuric acid that mass fraction is 95% are prepared
Acid solution；
(2) aluminum sulfate solution that the solution of zinc sulfate and concentration that compound concentration is 0.2mol/L are 0.2mol/L；
(3) beaker of 3 1L is taken, number consecutively 1-3 is added 20 mL of dilution heat of sulfuric acid of 2mol/L, is quickly stirring
While dilution heat of sulfuric acid, it is slowly added dropwise 200ml sodium silicate solution into three beakers respectively, with the dilute sulfuric acid of 2mol/L
Solution adjust reaction system pH to 4, then control speed of agitator be 100rpm(in the actual operation process, mixing speed can be set
It is scheduled within the scope of 80-120rpm) polymerization reaction 30min is carried out, obtained reaction solution is then stood into activation 15min to get arriving
Polysilicon acid solution.
(4) obtain polysilicon acid solution for above-mentioned, under agitation, respectively successively into three beakers instill 100mL,
Then the 0.2mol/L solution of zinc sulfate of 200 mL, 300mL successively instills the 0.2mol/ of 300mL, 200 mL, 100mL respectively
The aluminum sulfate solution of L is uniformly mixed, and in the actual operation process for 100rpm(, mixing speed can be set in control speed of agitator
Within the scope of 80-120rpm) polymerization reaction 30min is carried out, obtained reaction solution stands activation 20min to get aluminium silicate polymer zinc is arrived
Solution.
(5) above-mentioned aluminium silicate polymer zinc solution is uniformly mixed with polyacrylamide, calcium hydroxide and sodium hypochlorite respectively,
In, aluminium silicate polymer zinc solution be added is that 10000:6, aluminium silicate polymer zinc solution and hydroxide are calcareous with polyacrylamide mass ratio
Amount is than being that the mass ratio of 10000:6, aluminium silicate polymer zinc solution and sodium hypochlorite are similarly 10000:6；Then speed of agitator is controlled
In the actual operation process for 30 rpm, mixing speed can be set within the scope of 20-40rpm) polymerization reaction 20min is carried out, it obtains
The reaction solution arrived stands activation 10min, obtained aluminium silicate polymer zinc composite flocculation agent 1-3.
Embodiment 2
Prepare the simulated water sample that turbidity (NTU) is 120, preparation method are as follows: after kaolin powder is crossed 180 meshes, be placed in
100 DEG C of dry 2h in baking oven, then take the kaolin of suitable drying, are added to tap water under agitation: distilled water=1:
In the water of 1 (volume ratio), it is made into the suspension that NTU is 120, as simulated water sample.
Under agitation, the aluminium silicate polymer zinc composite flocculation agent 1- of the acquisition of embodiment 1 is separately added into simulated water sample
3, dosage 5ml/L first quickly stir 40 s with the speed of 200 r/min, then stir 30 with the speed of 30 r/min
Min, time of repose 1h.
Take away from clear liquid at liquid level 2cm, measure turbidity with HI 93703-11 type transmissometer, acquired results as shown in Figure 1,
Three kinds of flocculant turbidity removal rates are followed successively by 99.0%, 99.8%, 98.2% it can be seen from attached drawing 1, it is seen that the three of the preparation of embodiment 1
Kind aluminium silicate polymer zinc composite flocculation agent has flocculating effect, aluminium silicate polymer zinc composite flocculation agent Zn/Al molar ratio to simulated water sample
When for 1:1, turbid rate is gone to reach maximum value, increases or reduce Zn/Al molar ratio, turbid effect is gone to reduce instead, but remove
Rate can substantially be stablized 98% or more.
Embodiment 3
Take its water quality indicator of Zhengzhou municipal sewage plant bio-chemical effluent are as follows: with potassium dichromate method (GB11914-89) survey
Determining COD is 62 mg/L, with molybdate spectrophotometry (GB11893-89) measurement total phosphorus concentration for 1.12 mg/L, with gravimetric method
(GB11901-89) measurement suspended matter (SS) is 18.30mg/L.
For the aluminium silicate polymer zinc composite flocculation agent 1 for taking 10 mL embodiments 1 to be prepared in the beaker of 2 L, 1 L is added should
The water outlet of sewage treatment plant is first quickly stirred 30 s with the speed of 300 r/min, is then mixed slowly with the speed of 25 r/min
40min, time of repose 1.5h.It takes and is measured away from clear liquid at liquid level 2cm.Testing result COD is 16mg/L, total phosphorus 0.06
Mg/L, SS are 0.37 mg/L.It can be seen that COD removal rate can achieve 74%, total tp removal rate can achieve 95%, SS removal rate
It can achieve 98 %, effluent quality reaches " urban wastewater treatment firm pollutant emission standard " (GB18918-2002) level-one A mark
It is quasi-.
Embodiment 4
Take a certain dyeing waste water in Huaian, water quality indicator are as follows: COD 680mg/L, coloration are 500 times, SS 150mg/
L。
The aluminium silicate polymer zinc composite flocculation agent 2 that 10 mL embodiments 1 are prepared is placed in the beaker of 2 L, 1 L is added
The water outlet of the sewage treatment plant is first quickly stirred 30 s with the speed of 400 r/min, is then stirred at a slow speed with the speed of 40 r/min
Mix 25 min, time of repose 1h.It takes and is measured away from clear liquid at liquid level 2cm.
Measurement result COD is 306mg/L, and coloration is 120 times, and SS is 22.5 mg/L.COD removal rate can achieve
55%, coloration, which can achieve 78%, SS removal rate, can achieve 85 %.
Embodiment 5
The a certain paper mill paper waste in Hongze is taken, water quality indicator is that COD is 810mg/L, and coloration is 400 times, and SS is
600mg/L。
It is placed in the beaker of 2 L by the aluminium silicate polymer zinc composite flocculation agent 3 that 10 mL embodiments 1 are prepared, is added 1
The water outlet of the L sewage treatment plant first quickly stirs 40 s with the speed of 200 r/min, then at a slow speed with the speed of 30 r/min
Stir 30 min, time of repose 2h.
Measurement result COD is 243mg/L, and coloration is 120 times, and SS is 60 mg/L.It takes and is surveyed away from clear liquid at liquid level 2cm
It is fixed.COD removal rate can achieve 70%, and coloration, which can achieve 80%, SS removal rate, can achieve 90%.
Embodiment 6 prepares aluminium silicate polymer zinc composite flocculation agent
(1) sodium silicate solution of 0.3mol/L, the dilute sulphur for being 2mol/L by the diluting concentrated sulfuric acid that mass fraction is 95% are prepared
Acid solution；
(2) aluminum sulfate solution that the solution of zinc sulfate and concentration that compound concentration is 0.2mol/L are 0.2mol/L；
(3) 20 mL of dilution heat of sulfuric acid of 2mol/L is added in the beaker for taking 1 1L, in the same of quickly stirring dilution heat of sulfuric acid
When, it is slowly added dropwise 200ml sodium silicate solution into beaker, adjusts reaction system pH to 3, then controlling speed of agitator is
80r/min carries out polymerization reaction 50min, and obtained reaction solution stands activation 10min to get polysilicon acid solution is arrived.
(4) polysilicon acid solution is obtained by above-mentioned, under agitation, the 0.2mol/L sulfuric acid of 200 mL is instilled into beaker
Then zinc solution instills the aluminum sulfate solution of 200 mL 0.2mol/L, be uniformly mixed, and then controlling speed of agitator is 120r/
Min carries out polymerization reaction 10min, and obtained reaction solution stands activation 10min to get aluminium silicate polymer zinc solution is arrived.
(5) above-mentioned aluminium silicate polymer zinc solution is uniformly mixed with polyacrylamide, calcium hydroxide and sodium hypochlorite respectively, is gathered
The mass ratio of alumina silicate zinc solution and polyacrylamide, calcium hydroxide and sodium hypochlorite is 10000:4, and then control stirring turns
Speed is that 20 r/min carry out polymerization reaction 30min, and obtained reaction solution stands activation 40min, and obtained aluminium silicate polymer zinc is compound
Flocculant.
Take Nanjing municipal sewage plant bio-chemical effluent, water quality indicator: COD is 55 mg/L, and total phosphorus concentration is
1.30 mg/L, suspended matter (SS) are 16.30mg/L.
For the aluminium silicate polymer zinc composite flocculation agent for taking 10 mL the present embodiment to be prepared in the beaker of 2 L, 1 L is added should
The water outlet of sewage treatment plant is first quickly stirred 30 s with the speed of 200 r/min, is then mixed slowly with the speed of 30 r/min
30 min, time of repose 1h.It takes and is measured away from clear liquid at liquid level 2cm, detection COD removal rate can achieve 69%, total phosphorus ligands
Rate, which can achieve 92%, SS removal rate, can achieve 96 %, and effluent quality reaches " urban wastewater treatment firm pollutant emission standard "
(GB18918-2002) level-one A standard.
Embodiment 7 prepares aluminium silicate polymer zinc composite flocculation agent
(1) sodium silicate solution of 0.5mol/L, the dilute sulphur for being 2mol/L by the diluting concentrated sulfuric acid that mass fraction is 95% are prepared
Acid solution；
(2) aluminum sulfate solution that the solution of zinc sulfate and concentration that compound concentration is 0.2mol/L are 0.2mol/L；
(3) 20 mL of dilution heat of sulfuric acid of 2mol/L is added in the beaker for taking 1 1L, in the same of quickly stirring dilution heat of sulfuric acid
When, it is slowly added dropwise 200ml sodium silicate solution into beaker, adjusts reaction system pH to 2, then controlling speed of agitator is
120r/min carries out polymerization reaction 30min, and obtained reaction solution stands activation 20min to get polysilicon acid solution is arrived.
(4) polysilicon acid solution is obtained by above-mentioned, under agitation, the 0.2mol/L sulfuric acid of 200 mL is instilled into beaker
Then zinc solution instills the aluminum sulfate solution of the 0.2mol/L isometric (with zinc sulfate), be uniformly mixed；Controlling speed of agitator is
80r/min carries out polymerization reaction 30min, and obtained reaction solution stands activation 15min to get aluminium silicate polymer zinc solution is arrived.
(5) above-mentioned aluminium silicate polymer zinc solution is uniformly mixed with polyacrylamide, calcium hydroxide and sodium hypochlorite respectively, is gathered
The mass ratio of alumina silicate zinc solution and polyacrylamide, calcium hydroxide and sodium hypochlorite is 10000:8, and then control stirring turns
Speed is that 40 r/min carry out polymerization reaction 20min, and obtained reaction solution stands activation 30min, and obtained aluminium silicate polymer zinc is compound
Flocculant.
Take Wuxi municipal sewage plant bio-chemical effluent, water quality indicator: COD is 68 mg/L, and total phosphorus concentration is
1.09 mg/L, suspended matter (SS) are 19.24mg/L.
For the aluminium silicate polymer zinc composite flocculation agent for taking 10 mL the present embodiment to be prepared in the beaker of 2 L, 1 L is added should
The water outlet of sewage treatment plant is first quickly stirred 30 s with the speed of 200 r/min, is then mixed slowly with the speed of 30 r/min
30 min, time of repose 1h.It takes and is measured away from clear liquid at liquid level 2cm.
Detection COD removal rate can achieve 75%, and total tp removal rate, which can achieve 96%, SS removal rate, can achieve 95 %,
Effluent quality reaches " urban wastewater treatment firm pollutant emission standard " (GB18918-2002) level-one A standard.
The above embodiment is a preferred embodiment of the present invention, but embodiments of the present invention are not by above-described embodiment
Limitation, other any changes, modifications, substitutions, combinations, simplifications made without departing from the spirit and principles of the present invention,
It should be equivalent substitute mode, be included within the scope of the present invention.
Claims (2)
1. a kind of aluminium silicate polymer zinc composite flocculation agent, which is characterized in that the composite flocculation agent obtains by the following method:
A it is) 2mol/L sulfuric acid after 10:1 is mixed by volume by sodium metasilicate and concentration that concentration is 0.3-0.5mol/L, adjusts pH
It is stirred to react 30-50min for 2-4,80-120rpm, is then allowed to stand 10-20min, obtains polysilicon acid solution；
B the solution of zinc sulfate and aluminum sulfate solution that isometric concentration is 0.2mol/L) are successively added into polysilicon acid solution,
80-120rpm is stirred to react 10-30min, is then allowed to stand 10-20min, obtains aluminium silicate polymer zinc solution；
Polysilicon acid solution be added and solution of zinc sulfate volume ratio are 1:0.5-1.5, the body of polysilicon acid solution and solution of zinc sulfate
Product is than being 1:0.5-1.5；
C) aluminium silicate polymer zinc solution is uniformly mixed with polyacrylamide, calcium hydroxide and sodium hypochlorite, 20-40rpm stirring is anti-
20-30min is answered, 10-40min is then allowed to stand, is i.e. acquisition aluminium silicate polymer zinc composite flocculation agent；
Wherein, identical in quality, the aluminium silicate polymer zinc solution and poly- third for polyacrylamide, calcium hydroxide and the sodium hypochlorite being added
The mass ratio of acrylamide, calcium hydroxide and sodium hypochlorite is 10000:6.
2. application of the aluminium silicate polymer zinc composite flocculation agent as described in claim 1 in Treating Municipal Sewage and industrial wastewater, institute
State in Treating Municipal Sewage and industrial wastewater application refer to, by volume by the aluminium silicate polymer zinc composite flocculation agent
0.5%-1% is put into sewage, is first stirred to react 30-40s with the speed of 200-400rpm, then anti-with the speed stirring of 25-40rpm
25-40 min is answered, 1-2h is then allowed to stand, that is, realizes the decoloration turbidity removal decarburization to municipal sewage and industrial wastewater.
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| CN112358021A (en) * | 2020-12-31 | 2021-02-12 | 常州市五洲化工有限公司 | Preparation method of composite coagulant |
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